JP6549937B2 - LAMINATED SHEET AND MOLDED BODY, AND METHOD FOR MANUFACTURING THEM - Google Patents

Description

  The present invention relates to a laminated sheet, a molded body using the same, and a method of manufacturing the same.

  Conventionally, laminated sheets are used to decorate various parts such as home appliances, automobiles, office automation equipment, and construction materials. For example, it is practiced to increase the added value of the part by forming a laminated sheet on which the pattern of metal hairline tone, wood grain tone, carbon cloth tone, etc. is given on the surface of the component (molded body).

  Recently, in order to further increase the added value, products have been developed to be closer to real metal hairlines, grain patterns, carbon cloths and the like. For example, parts having a three-dimensional design such as metal hairline tone, wood grain tone, carbon cloth tone, etc. are preferred by giving the surface an uneven surface shape. These parts may be manufactured by film insert molding. In the film insert molding method, first, a shaped body in which a laminated sheet provided with a desired pattern is shaped into a desired part surface shape is manufactured using a thermoforming method such as vacuum molding or pressure forming. Next, the shaped body and the resin molded body are integrated by placing the shaped body in the mold cavity and injecting the molten resin.

  As a method of giving a pattern having a three-dimensional effect on the part surface, a method of giving an irregular surface shape by embossing etc. in advance to the laminated sheet surface, or embossing processing on the inner surface of the mold cavity and applying film embossing on the surface There is a method of providing the uneven surface shape and the like. However, in the case of the former, the uneven surface shape of the surface can not often be maintained by heat or pressure received at the time of thermoforming at the time of producing a shaped body or film insert molding. In the latter case, when changing the design, a die is required for each design, and there is a problem that the manufacturing cost becomes high. Moreover, as for the uneven | corrugated surface shape obtained by these methods, an unevenness | corrugation may lose | disappear by a scratch during use by a desired use.

  In order to solve these problems, a method has been proposed in which a design layer is laminated on the back side of a transparent substrate film having a smooth surface, and a concavo-convex surface shape is provided to the design layer and the transparent base film from the back side. . In addition, a transparent protective layer is applied to the surface of the laminate sheet having the irregular surface shape on the surface having the irregular surface shape, and the surface of the protective layer is covered with a smooth transparent sheet by film insert molding. A method has been proposed. According to these methods, while maintaining the three-dimensional effect of the pattern layer during the production of the resin molded product, it is also effective for preventing the disappearance of the uneven surface shape due to the damage during use (Patent Document 1) And Patent Document 2). However, in order to give the design having a three-dimensional effect to the pattern layer, these methods first use a printing method such as gravure printing or screen printing on a printing original fabric or substrate film having a smooth surface. Is laminated, and embossed to form an uneven surface shape on a printing original fabric or a base film including a pattern layer. Therefore, although it is a design having a three-dimensional effect, there is almost no transparency of the pattern layer itself, and the change in thickness of the pattern layer itself is scarce, so that no sense of depth is felt in the pattern layer.

  On the other hand, there is also one in which a convex flat pattern portion having a flat uniform height (thickness) having transparency by a printing method such as gravure printing or screen printing is partially formed on the base sheet instead of the entire surface (Patent Document 3) reference). In this case, a concavo-convex shape is formed by the convex-shaped pattern part partially configured on the base sheet and the other part, to obtain a design having a three-dimensional effect. However, since the convex pattern portion is a flat portion having a constant height (thickness), the perceived three-dimensional effect is monotonous. Moreover, since the convex part of patent document 3 does not have a change of height (thickness), the composite change of a pattern layer and a colored layer is scarce, and even if there is depth, the change (sense of depth) is scarce.

  It is not a monotonous design with a three-dimensional effect as described above but with no change in thickness in the pattern layer itself and a poor sense of depth, but a three-dimensional effect and its change in the pattern layer, and furthermore a design with a sense of depth Is required. In addition, a design with irregular 3D effect such as real metal hairline, wood grain, carbon cloth, etc., and a sense of depth, or a combination of a natural product and a processed product, also has a 3D effect and its change and depth. It is required to express a new design.

Unexamined-Japanese-Patent No. 2010-82912 JP 2012-51218 A Patent No. 3003034

  The present embodiment solves the problems as described above, and when integrated with a molded resin layer by a molding method such as injection molding, the surface of the molded body is smooth and the aim is a three-dimensional effect and its change, Furthermore, it is an object of the present invention to provide a laminated sheet capable of expressing a design having a sense of depth, and a molded body in which the laminated sheet is integrated with a molded resin layer.

  In the first embodiment, a resin layer having light permeability and having a softening temperature of 120 ° C. or less, a colored layer laminated on one surface of the resin layer, having a softening temperature of 120 ° C. or less, and The pattern includes a backing layer laminated on the colored layer and having a softening temperature of 120 ° C. or less, and a pattern layer laminated on the other surface of the resin layer and made of an ionizing radiation curable resin and having light transmittance. It is a lamination sheet in which the softening temperature of a layer is 140-160 ° C, and the surface of the above-mentioned picture layer made a concavo-convex field shape, and thickness changed continuously.

  In the second embodiment, a colored layer having a softening temperature of 120 ° C. or less and a softening temperature of 120 ° C. or less are provided on one surface of a resin layer having light permeability and a softening temperature of 120 ° C. or less. The backing layer is sequentially laminated, and then the ionizing radiation curable resin ink is applied to the other surface of the resin layer, and the ionizing radiation curable resin ink is irradiated with the ionizing radiation to have light transparency and softening. It is a manufacturing method of a lamination sheet which temperature is 140-160 ° C, and the surface makes a concavo-convex field shape, and forms a picture layer where thickness changed continuously.

  The third embodiment includes the laminated sheet and a molded resin layer integrated with the laminated sheet, the surface of the pattern layer is smooth, and the backing layer is in contact with the molded resin layer. , Molded body.

  The fourth embodiment is a method of manufacturing the molded article, wherein the laminated sheet is disposed in a mold cavity with the pattern layer side facing the mold cavity surface, and the backing layer side of the laminated sheet is disposed. A resin is injected, and the molded resin layer is molded while pressing the pattern layer side against the mold cavity surface.

  According to the present embodiment, when integrated with the molding resin layer by a molding method such as injection molding, the surface of the molding is smooth, yet has a sense of three-dimensionality and its change, and a sense of depth. The laminated sheet which can express a design, and the molded object with which the said laminated sheet was integrated with the molding resin layer can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows typically the lamination sheet which concerns on one Embodiment. It is a figure which shows an example of the micro cross section in the pattern layer of this lamination sheet. It is a cross-sectional schematic diagram which shows typically one Embodiment of the molded object with which this lamination sheet was integrated with the molding resin layer. It is a figure which shows an example of the micro cross section in the pattern layer of this molded object. It is a figure which shows an example of reflection of the light ray in this molded object. It is a figure which shows a grain pattern image and its gray scale conversion. It is digital data explanatory drawing of a grain pattern. It is sectional drawing at the time of shaping | molding of the molded object using this lamination sheet. It is a cross-sectional schematic diagram which shows typically the molded object obtained by Comparative Example 1 and 2. FIG.

  Hereinafter, the present embodiment will be described in detail with reference to the drawings.

  FIG. 1 schematically shows a cross section of a laminated sheet according to an embodiment. In the laminated sheet 1, the colored layer 3 and the backing layer 4 are sequentially laminated on one side of the light-transmitting resin layer 2, and the other side of the resin layer 2 is made of light-transmitting resin made of ionizing radiation curable resin. It is a laminated sheet in which the pattern layer 5 is laminated, and the surface of the pattern layer 5 has an uneven surface shape, and the thickness of the pattern layer 5 is continuously changed. As a method of manufacturing the laminated sheet 1, after the colored layer 3 and the backing layer 4 are sequentially laminated on one surface of the resin layer 2, an ionizing radiation curable resin ink is applied to the other surface of the resin layer 2 to ionize There is a method of forming the picture layer 5 by irradiating the radiation curable resin ink with ionizing radiation. In the present specification, the surface of the pattern layer is the front surface of the pattern layer. Similarly, the surface of the molded body is the front surface of the molded body.

  The resin layer 2 is a sheet-like material having light transmittance, and a commercially available film may be used, or the resin may be cured and used. When the resin layer 2 has light transmittance, the colored layer 3 can be viewed through the pattern layer 5 and the resin layer 2, and furthermore, the thickness of the pattern layer 5 and the resin layer 2 can be viewed. The light transmittance of the resin layer 2 is preferably 80% or more in the wavelength range of 400 to 700 nm.

  Examples of the resin that forms the resin layer 2 include acrylic resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, acrylonitrile butadiene styrene resins, polyethylene resins, polypropylene resins, polystyrene resins, and polychlorinated resins. Thermoplastic resins such as vinyl resins and thermosetting resins such as polyurethane resins and unsaturated polyester resins can be mentioned. The resin layer 2 may be a composite or laminate of two or more of these resins. The composite refers to a resin layer composed of a mixture of two or more types of resins, and the laminate refers to a resin layer formed by laminating two or more types of resin layers having different resin compositions. Among them, thermoplastic resins are preferable from the viewpoint of ease of thermoforming, and specifically, acrylic resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, acrylonitrile butadiene styrene At least one resin selected from the group consisting of polyethylene resins, polyethylene resins, polypropylene resins, polystyrene resins, and polyvinyl chloride resins, or a composite or laminate of two or more resins Is preferred.

  In addition, the resin forming the resin layer 2 may further contain a dispersant, a thermal stabilizer, a thermal radical polymerization inhibitor, a light stabilizer, an antioxidant, an antiseptic, a pH adjuster, an antifoamer, and a penetration, as required. You may add additives, such as an agent.

  In addition, the resin layer 2 may be colored using a coloring agent such as one or more types of pigments and dyes to such an extent that light transmission is not inhibited. In addition, the entire surface may be the same color or partial color, or may be partially different color. When weather resistance and light resistance are required, it is preferable to use a pigment.

  The thickness of the resin layer 2 is not particularly limited, and is preferably 50 to 200 μm. When the thickness is 50 μm or more, the strength can be increased to improve the handleability at the time of post-processing, and the sense of depth can be improved. By being 200 micrometers or less, since a thermoforming fall can be suppressed, it is easy to shape in an exact shape. The thickness of the resin layer 2 is more preferably 50 to 150 μm. The thickness of the resin layer 2 is preferably constant.

  The softening temperature of the resin layer 2 is 120 ° C. or less, and preferably 100 ° C. or less. When the molded product 7 is formed by a molding method such as injection molding because the softening temperature is 120 ° C. or lower, the resin layer 2 is deformed so as to sink in, and the uneven surface shape of the surface of the pattern layer 5 is smoothed. It becomes easy to be deformed to the surface. The lower limit of the softening temperature of the resin layer 2 is not particularly limited, and may be, for example, 80 ° C. or more.

  The colored layer 3 is a layer for coloring the laminated sheet 1. The three-dimensional effect can be improved by reflecting the colored layer 3 without transmitting light. In addition, the formation method of the colored layer 3 is not specifically limited, For example, you may laminate | stack on the resin layer 2 using well-known coating machines, such as a reverse roll coater, a knife coater, or a comma coater.

  Examples of the resin that forms the colored layer 3 include thermoplastic resins such as polyester resins, acrylic resins, and vinyl chloride resins. Alternatively, a composite or laminate of these two or more resins may be used.

  The colored layer 3 is colored using a colorant such as one or more types of pigments and dyes. When weather resistance and light resistance are required, it is preferable to use a pigment. Organic and inorganic pigments can be used as the pigment. Examples of organic pigments include nitroso, dyed lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, dioxazines And isoindolines, azomethines, pyrrolopyrroles and the like. As the inorganic pigment, for example, oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black), metal powders Etc.

  The color of the colored layer 3 is not particularly limited, but from the viewpoint of improving the three-dimensional effect, it contains a glittering pigment to make it easier to reflect light at the interface of the concavo-convex shape with the resin layer 2. Is preferred. Alternatively, the colored layer 3 may be a composite colored layer in which a metal deposition film having an effect of reflecting light in addition to the colored layer is stacked. In the case of the composite colored layer, it is sufficient that a part thereof is colored. For example, a metallic vapor deposition film may be laminated on a transparent layer which is not intentionally colored to emphasize metal tone.

  As a lustrous pigment, two can be mentioned as a typical thing, the metallic pigment which expresses metallic glossiness, and the pearl pigment which expresses pearlic glossiness. The metallic pigment may, for example, be a powder or flake of a metal such as aluminum or copper, a powder or flake of an alloy such as brass, or a finely cut strip of a metallized film. Pearl pigments include natural mica or synthetic mica coated with one or two or more metal oxides such as titanium oxide, silicon oxide, iron oxide, etc., fine fragments of a film laminated with layers of resins different in light refraction, and pearl powder , Powder of shell inner wall, fish scale foil, etc.

  Moreover, you may add additives, such as a dispersing agent, a heat stabilizer, an antioxidant, antiseptic | preservative, a pH adjuster, an antifoamer, a penetrant, to the colored layer 3 as needed.

  The light transmittance of the colored layer 3 is preferably lower than the light transmittance of the resin layer 2 and the pattern layer 5 from the viewpoint of improving the three-dimensional effect. That is, the three-dimensional effect is obtained by the light transmitted through the pattern layer 5 and the resin layer 2 being reflected by the colored layer 3. Therefore, it is desirable not to transmit light up to the backing layer 4 which is the lower layer, that is, to hide or shield the backing layer 4 by the colored layer 3. The light transmittance of the colored layer 3 is preferably 10% or less, more preferably 5% or less, and further preferably 0% in the wavelength range of 400 to 700 nm from the viewpoint of the concealability. preferable.

  The thickness of the colored layer 3 is not particularly limited, and is preferably 20 to 80 μm. By being 20 micrometers or more, it is excellent in concealability. By being 80 micrometers or less, since a thermoforming fall can be suppressed, it is easy to shape in an exact shape. The thickness of the colored layer 3 is more preferably 30 to 60 μm. The thickness of the colored layer 3 is preferably constant.

  The softening temperature of the colored layer 3 is 120 ° C. or less, and preferably 100 ° C. or less. Since the softening temperature is 120 ° C. or less, when the molded body 7 is formed by a molding method such as injection molding, the uneven surface shape of the surface of the pattern layer 5 is easily deformed to a smooth surface. Therefore, the resin layer 2 and the colored layer 3 are easily deformed into a sunk shape as the uneven surface shape of the surface of the pattern layer 5 is deformed into a smooth surface. The lower limit of the softening temperature of the colored layer 3 is not particularly limited, and may be, for example, 80 ° C. or more.

  The backing layer 4 is a layer for melt adhesion (adhesion) with the resin forming the molded resin layer 6 when producing the molded body 7 by a molding method such as injection molding. Moreover, it is a layer for protecting the colored layer 3 which is one of the layers which comprise the lamination sheet 1. FIG. In addition, the formation method of the backing layer 4 is not specifically limited, For example, you may form by laminating a resin sheet on the surface of the colored layer 3 by heat lamination process etc.

  The resin forming the backing layer 4 is, for example, acrylic resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, acrylonitrile butadiene styrene resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride Examples thereof include thermoplastic resins such as based resins, and thermosetting resins such as polyurethane based resins and unsaturated polyester based resins. Further, a composite or laminate of two or more of these resins may be used. Among them, thermoplastic resins are preferable from the viewpoint of easiness of thermoforming and protection of the colored layer 3, and specifically, acrylic resins, polycarbonate resins, acrylonitrile butadiene styrene resins, polyethylene It is preferable that it is a composite or a laminate of any one resin selected from the group consisting of a base resin, a polypropylene resin, a polystyrene resin, and a polyvinyl chloride resin, or two or more resins.

  Further, from the viewpoint of adhesion when forming the molded body 7, a resin used for the molded body 7 manufactured by a molding method such as injection molding, that is, a thermoplastic resin similar to the resin forming the molded resin layer 6 is preferable.

  The thickness of the backing layer 4 is not particularly limited, and is preferably 200 to 400 μm. By being 200 μm or more, the colored layer 3 can be protected from damage such as heat and pressure at the time of molding. By being 400 micrometers or less, since a thermoforming fall can be suppressed, it is easy to shape in an exact shape. The thickness of the backing layer 4 is more preferably 200 to 300 μm. It is preferable that the thickness of the backing layer 4 be constant.

  The softening temperature of the backing layer 4 is 120 ° C. or less, preferably 100 ° C. or less, and more preferably 90 ° C. or less. Since the softening temperature is 120 ° C. or less, when the molded body 7 is formed by a molding method such as injection molding, the uneven surface shape of the surface of the pattern layer 5 is easily deformed to a smooth surface. Therefore, the resin layer 2, the colored layer 3 and the backing layer 4 are easily deformed into a sunken shape as the shape of the uneven surface of the surface of the pattern layer 5 changes to a smooth surface. The softening temperature of the backing layer 4 is preferably lower than the softening temperatures of the resin layer 2 and the colored layer 3. Thereby, even when the thickness of the backing layer 4 is thicker than the thicknesses of the resin layer 2 and the colored layer 3, the interface between the pattern layer 5 and the resin layer 2 when forming the molded body 7 by a molding method such as injection molding, And the interface between the resin layer 2 and the colored layer 3 and the interface between the colored layer 3 and the backing layer 4 can be in the form of an irregular surface parallel to each other. The lower limit of the softening temperature of the backing layer 4 is not particularly limited, and may be, for example, 60 ° C. or more.

  The picture layer 5 is a layer for giving a picture (here, the picture is a concept including a picture and a pattern) to the laminated sheet 1. When making molded object 7 by a molding method such as injection molding, the resin layer 2, the colored layer 3, and the backing layer 4 are deformed by making the pattern layer a layer having a change in thickness (a layer having unevenness). It can be done.

  The resin which forms the picture layer 5 is a cured resin having light transmittance and is an ionizing radiation curable resin. The ionizing radiation curable resin can easily obtain a surface having an uneven surface shape in a short time, and is suitable for applications involving processing productivity. By forming a surface having an uneven surface shape, the boundary surface between the pattern layer 5 and the resin layer 2 and the boundary surface between the resin layer 2 and the colored layer 3 are deformed into an uneven surface shape when molding the molded resin layer 6 as described later. It is possible to As the boundary surface is deformed into a concavo-convex shape in this way, irregular reflection of incident light occurs, and the resin layer 2 and the colored layer seen through the pattern layer 5 with only a slight change in the incident angle and the viewing position of the light. The composite appearance of 3 changes. Therefore, it is possible to express a unique design by combining the sense of depth due to the change in the thickness of the pattern layer itself and the three-dimensional effect felt by the irregular reflection of light by the curved surface of the uneven surface shape.

  As the ionizing radiation curable resin, known ultraviolet curable resins and electron beam curable resins can be used. For example, those having an acrylic functional group are preferable, and in view of high versatility and being able to obtain a wide variety of cured resins, acrylic UV curable resins are more preferable. An acrylic UV curable resin is basically composed of a photopolymerization initiator, a reactive monomer, and a reactive oligomer. By irradiation with ultraviolet light, the photopolymerization initiator becomes a radical, which activates the functional groups of the reactive monomer and the reactive oligomer, and combines them one after another in a chain to convert into a polymer (acrylic resin) .

  The softening temperature of the picture layer 5 is 140 to 160 ° C. By being in this range, the laminated sheet 1 can be easily formed into a desired design shape using a thermoforming method such as vacuum forming or air pressure forming, or when the molded body 7 is formed by a forming method such as injection molding The uneven surface shape of the surface of the pattern layer 5 is easily deformed into a smooth surface. That is, when the softening temperature is 140 ° C. or more, the pattern layer 5 is easily deformed into a smooth surface while maintaining its own continuous thickness change at the time of forming the formed body 7. Moreover, by being 160 degrees C or less, it is easy to shape the lamination sheet 1 into a desired design shape using a thermoforming method.

  The picture layer 5 is preferably colored to such an extent that the light transmission is not impaired, using a coloring agent such as one or more kinds of pigments and dyes. In addition, the entire surface may be the same color or partial color, or may be partially different color. When weather resistance and light resistance are required, it is preferable to use a pigment. The pigment may be used either organic or inorganic. Examples of organic pigments include nitroso, dyed lakes, azo lakes, insoluble azos, monoazos, disazos, condensed azos, benzimidazolones, phthalocyanines, anthraquinones, perylenes, quinacridones, dioxazines And isoindolines, azomethines, pyrrolopyrroles and the like. As the inorganic pigment, for example, oxides, hydroxides, sulfides, ferrocyanides, chromates, carbonates, silicates, phosphates, carbons (carbon black), metal powders Etc.

  In the picture layer 5, as necessary, a sensitizer for accelerating the initiation reaction of the photopolymerization initiator, a dispersant, a heat stabilizer, a thermal radical polymerization inhibitor, an antioxidant, a preservative, pH adjustment Additives such as an agent, an antifoaming agent, and a penetrant may be added.

  A design having a composite appearance with the resin layer 2 and the colored layer 3 is obtained by incorporating a coloring agent such as a pigment in the pattern layer 5 and forming the colored pattern layer 5 while securing light transmittance. be able to. That is, when the resin layer 2 and the colored layer 3 are viewed from the side of the pattern layer 5, the color of the pattern layer 5 itself and the color of the resin layer 2 and the colored layer 3 thereunder are overlapped. For example, by coloring the light color in the pattern layer 5 and coloring the resin layer 2 or the colored layer 3 below it in a dark color, the thickness of the pattern layer 5 is felt while overlapping with the color of the resin layer 2 or the colored layer 3 It is a design that makes it easy to clearly recognize the three-dimensional effect and its change, and also the sense of depth. Moreover, even if the pattern layer 5 is colorless and transparent, it is possible to sense the change in thickness of the pattern layer by light reflection, and to obtain the same effect.

  In addition, it is preferable that the laminated body which united the resin layer 2 and the pattern layer 5 has the light transmittance of 10% or more in the range of wavelength 400-700 nm in the at least one part. Furthermore, in the laminate, the light transmittance may be different in each part, and by changing the light transmittance in this manner, the sense of depth can be enhanced. Moreover, you may have a part which does not give a feeling of depth as needed. The light transmittance of this portion is preferably less than 10%. By mixing a portion having a sense of depth and a portion having no sense of depth, it is possible to obtain a design rich in variation as the entire design. In addition, when the part which has a sense of depth and the part which does not have are mixed, in the case of the measurement of light transmittance, it divides into the part which has a sense of depth, and a part which does not have and measures ten places each, and each light transmittance is all It is preferably 10% or more and less than 10%.

  The surface of the pattern layer 5 has an uneven surface shape, and the boundary surface with the resin layer 2 is smooth. Therefore, the thickness of the pattern layer 5 is not constant but changes continuously. As a result, even when the coloring density of the pattern layer 5 is constant, the apparent density due to a change in thickness can be obtained (the above-mentioned pattern layer 5, the resin layer 2 and the colored layer 3 form a composite appearance). Differences in color intensity). Therefore, it is possible to express a design that feels more three-dimensional, its change, and even a sense of depth. The thickness of the pattern layer 5 is not particularly limited, and can be set in accordance with the required design. The thickness of the pattern layer 5 according to one embodiment may be 5 to 50 μm or 10 to 30 μm in thickness of the thinnest portion (thinnest portion). Moreover, 30-150 micrometers may be sufficient as the thickness of the thickest part (thickest part), and 50-100 micrometers may be sufficient.

  In the present embodiment, in the pattern layer 5 whose thickness continuously changes, a plurality of curves having curvature radii different in the upper side of the cross section are connected. That is, in the cross section obtained by cutting the pattern layer 5 in the thickness direction, the upper side of the pattern layer 5 has a shape in which curves having different radii of curvature are connected. The radius of curvature of a plurality of curves constituting the upper side of the cross section of the picture layer 5 is preferably in the range of, for example, 17.5 μm to 100 mm, and may be in the range of 17.5 to 1000 μm.

  Moreover, in this embodiment, the cross-sectional shape of the pattern layer 5 in the several cross section which is parallel mutually differs between the pattern layers 5 which change thickness continuously. That is, the cross-sectional shape in an arbitrary cross section of the picture layer 5 changes continuously. This is explained in detail below.

  Consider an arbitrary cross section (a) in the picture layer 5 shown in FIG. An example is shown in FIG. The cross section (a) shows the thickness of the pattern layer 5 perpendicular to the straight line (b) of length w formed on the surface of the pattern layer 5 in contact with the resin layer 2 and both ends of the straight line (b). A straight line (c) of length h1 extending in the longitudinal direction, a straight line (d) of length h2 and a curve (e) formed by a series of curves having different radii of curvature formed on the surface of the picture layer 5 It has a shape that Next, when a cross section (g) separated from the cross section (a) by a minute distance (Δf) and in parallel with the cross section (a) is considered, the cross section (g) is a straight line of length w (b ′) And a straight line (c ') of length h1' extending straight from both ends of the straight line (b ') in the thickness direction of the pattern layer 5 and a straight line (d') of length h2 'and the surface of the pattern layer 5 And a curve (e ') formed by a series of curves having different radii of curvature. In this embodiment, (1) the lengths of the straight lines (c) and (c ′) are different (h1 ≠ h1 ′), and (2) the lengths of the straight lines (d) and (d ′) are different (h2 ≠ h2 ') Or (3) It has a structure satisfying at least one or more of the three or more of which the radius of curvature of the individual curves constituting the curves (e) and (e') and the lengths of the curves are different. In other words, when comparing the two cross sections described above, among the three straight lines and one curve constituting each cross section, the lengths of the two straight lines in the thickness direction and the difference formed on the surface of the pattern layer 5 At least any one of the curves formed by connecting the curvature radius curves is different between the two cross sections (a) and (g). That is, this means that the cross-sectional shapes of the cross section (a) and the cross section (g) are different, and the pattern layer 5 of which thickness is continuously changed which constitutes the laminated sheet 1 of this embodiment is an arbitrary pattern having a constant width w. The cross-sectional shape in the cross section changes continuously. The cross-sectional areas of the cross section (a) and the cross section (g) may be the same or different, but preferably the cross-sectional shape and the cross-sectional area are different, and the cross-sectional shape and the cross-sectional area preferably change continuously. Such a change occurs at a minute distance, and there may be cases where the cross-sectional shape and the cross-sectional area are the same over a wide area. Here, w can be set, for example, to 500 μm, and the minute distance (Δf) is, for example, in the range of 35 to 70 μm.

  The method for laminating the picture layer 5 is not particularly limited. It can be laminated by methods such as screen printing, gravure printing, inkjet printing and the like which are conventionally known printing methods. Among them, inkjet printing is preferable because it is relatively easy to continuously change the cross-sectional shape and the cross-sectional area of an arbitrary cross section of the picture layer 5.

  The laminated sheet 1 obtained as described above is integrated with the molded resin layer 6 using the following molding method to form a molded body 7.

  Injection molding is preferable as a molding method for integrating the laminated sheet 1 with the molding resin layer 6 to form the molding 7. Injection molding includes injection compression molding, injection press molding, and the like in addition to general injection molding. As a processing method of the molded object 7 according to one embodiment, a film insert molding method in which the laminated sheet 1 is pre-shaped in the first step, and injection molding is performed using the laminated sheet 1 pre-shaped in the second step thereafter. Can be mentioned.

  In the preliminary shaping in the first step, a shaped body is fabricated by shaping the laminated sheet 1 into a desired design shape using a thermoforming method such as vacuum forming or pressure forming. Here, the vacuum forming is a method of preheating the decorative film to a temperature at which it can be thermally deformed in advance, suctioning it into the mold by pressure reduction, and pressure-cooling and forming the mold while drawing. The pressure forming is a method in which the decorative film is preheated to a temperature at which it can be thermally deformed in advance, pressed from the opposite side of the mold, and compression-cooled to the mold for molding. These depressurization and pressurization may be performed simultaneously.

  In the injection molding of the second step, the shaped body is placed in the mold cavity and the molten resin is injected to integrate the shaped body and the molded resin layer 6. Specifically, in injection molding, as shown in FIG. 8, the laminated sheet 1 is placed in the cavity 11 of the mold 10 with the pattern layer 5 side facing the mold cavity surface 12, and the mold 10 is closed. After that, the resin is injected and injected through the gate portion 13 to the backing layer 4 side of the laminated sheet 1. Therefore, the molded resin layer 6 is molded while pressing the pattern layer 5 side of the laminated sheet 1 against the mold cavity surface 12. Thereby, the said molded object 7 with which the lamination sheet 1 was integrated with the molding resin layer 6 is obtained. The temperature of the molten resin at the time of injection molding may be, for example, 180 to 320 ° C. or 200 to 300 ° C.

  The resin used for the molded body 7, that is, the resin for forming the molded resin layer 6 is not particularly limited. For example, polyolefin resins such as polyethylene and polypropylene, polystyrene resins, polyvinyl chloride resins, poly ( Well-known thermoplastic resins such as methacrylate resins, acrylic resins, polyacetal resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polycarbonate resins, polyphenylene sulfide resins and polyimide resins It can be used. These resins may be used alone or in combination of two or more.

  As shown in FIG. 3, in the obtained molded body 7, the surface of the pattern layer 5 is smooth, and the backing layer 4 is in contact with the molded resin layer 6. In addition, the interface between the picture layer 5 and the resin layer 2, the interface between the resin layer 2 and the colored layer 3, and the interface between the colored layer 3 and the backing layer 4 have a concavo-convex surface shape parallel to each other. . The reason for such a shape will be described.

  As shown in FIG. 1, the pattern layer 5 has an uneven surface on the side not in contact with the resin layer 2 until the molded body 7 is formed, that is, on the surface side. However, when forming the molded body 7 by a molding method such as injection molding, the laminated sheet 1 is softened under the influence of the resin forming the molded resin layer 6 of high temperature and high pressure injected and injected to the backing layer 4 side. The side is pressed against the mold cavity surface 12. At this time, the irregularities on the surface of the pattern layer 5 in contact with the mold cavity surface 12 become smooth so as to follow the mold cavity surface 12 finished to be smooth.

  On the other hand, the other layer group constituting the laminate sheet 1, that is, the layer group including the resin layer 2, the colored layer 3 and the backing layer 4 is a material having a softening temperature lower than that of the pattern layer 5. Therefore, since the other layer group is softened more while the surface which had the uneven surface is smoothed, the pattern layer 5 will be buried in the layer group. That is, the convex portion on the surface of the pattern layer 5 is pressed against the mold cavity surface 12 and pushed to the same position as the concave portion and becomes smooth, and at the same time, on the resin layer 2 side in contact with the pattern layer 5 on the other side. The convex shape of the pattern layer 5 is formed. Originally, the pattern layer 5 had an uneven surface on the side not in contact with the resin layer 2, but the boundary surface between the pattern layer 5 and the resin layer 2 inevitably deforms into an uneven surface shape by this deformation. Furthermore, the boundary surface between the resin layer 2 and the colored layer 3 is similarly deformed to the uneven surface shape. Here, since the thickness of the resin layer 2 is constant, the boundary surface between the resin layer 2 and the colored layer 3 and the boundary surface between the pattern layer 5 and the resin layer 2 have an uneven surface shape parallel to each other.

  Similarly, deformation extends to the interface between the colored layer 3 and the backing layer 4 and the interface between the backing layer 4 and the molding resin layer 6. That is, the boundary surface between the colored layer 3 and the backing layer 4 and the boundary surface between the backing layer 4 and the molded resin layer 6 also have an uneven surface shape parallel to the boundary surface between the pattern layer 5 and the resin layer 2. Therefore, when the laminate sheet 1 is formed into a molded body 7 by a molding method such as injection molding, the surface of the pattern layer 5 is smooth as shown in FIG. 3 and the interface between the pattern layer 5 and the resin layer 2 and the resin layer 2 The interface between the color filter and the colored layer 3 and the interface between the color layer 3 and the backing layer 4 are in the form of an irregular surface parallel to each other (that is, separated by a predetermined distance).

  By continuously changing the thickness of the pattern layer 5 in this manner, the interface between the resin layer 2 and the colored layer 3 has a curved surface with various normal directions as shown in FIG. Surface shape. When light strikes such a curved surface, it reflects diffusely in various directions, and the incident angle of the light and the viewing position change slightly, and the composite appearance of the resin layer 2 and the colored layer 3 can be seen through the pattern layer 5 One changes. Therefore, it is possible to express a unique design by combining a sense of depth due to a change in thickness of the pattern layer itself and a three-dimensional effect felt by irregular reflection of light on the curved surface of the uneven surface shape.

  The thickness of the pattern layer 5 changes continuously at the stage when the formed body 7 is formed, and the cross-sectional shapes of the pattern layer 5 in a plurality of cross sections parallel to each other are different. Same as before formation. However, after the formation of the molded body 7, the surface of the pattern layer 5 is smooth, and the interface with the resin layer 2 has an irregular surface shape. Therefore, the shape of the pattern layer 5 after the formation of the molded body 7 is as follows with reference to FIG. That is, in the arbitrary cross section (A) of the pattern layer 5, the straight line (B) of length w formed on the surface of the pattern layer 5 and the thickness direction of the pattern layer 5 vertically from both ends of the straight line (B) Curve (E) of a straight line (C) of length H1 and a straight line (D) of length H2 and a curve with different radius of curvature formed on the interface between the pattern layer 5 and the resin layer 2 And has a shape composed of Further, the cross section (G) which is separated from this cross section (A) by a minute distance (Δf) and is in parallel with the cross section (A) is straight line (B ') of length w and both ends of the straight line (B') A straight line (C ') of length H1' extending in the thickness direction of the pattern layer 5 and a straight line (D ') of length H2' extending vertically in the thickness direction of the pattern layer 5 and different formed at the interface between the pattern layer 5 and the resin layer 2 It consists of a curve (E ') formed by a series of curves having a radius of curvature. In this embodiment, (1) lengths of straight lines (C) and (C ′) are different (H1 ≠ H1 ′), (2) lengths of straight lines (D) and (D ′) are different (H2 ≠ H2 ') Or (3) It has a structure satisfying at least one or more of the three or more different in the radius of curvature and the length of the individual curves constituting the curves (E) and (E'). Accordingly, the cross-sectional shapes of the cross-section (A) and the cross-section (G) are different, that is, the pattern layer 5 of the molded body 7 of the present embodiment, of which thickness varies continuously, is The cross sectional shape (preferably, the cross sectional shape and the cross sectional area) changes continuously. The dimensions of w and Δf are the same as in the case of the laminated sheet 1 described above.

  The application of the molded body 7 is not particularly limited. For example, the molded body 7 can be used as constituting various products or parts such as home appliances, interior parts of automobiles, communication devices, OA devices, building materials and the like.

  In the present specification, the measurement of the light transmittance, the thickness, and the softening temperature of each layer is performed as follows.

Light transmittance: Only the layer to be measured among the laminated sheets is formed into a film by itself, and the obtained film is used to measure by a spectrophotometer (CM-3600 d, manufactured by Konica Minolta Co., Ltd.) Measure the spectrum of light transmittance. Let thickness of the film to produce be the thickness in the lamination sheet of the layer used as a measuring object. The measurement is performed in the wavelength range of 400 to 700 nm, and the average value in the range is determined. Ten films are prepared for each layer, measured, and the light transmittance is determined by calculating the average value of these. In addition, about the light transmittance of the laminated body which united the resin layer and the pattern layer, the laminated body which laminated | stacked the resin layer and the pattern layer in the shape of a film according to each thickness in a lamination sheet is produced and measured.

Thickness: The vertical cross section of the laminated sheet 1 is observed with a microscope (Digital HF microscope VH-8000, manufactured by Keyence Corporation), and the thickness of the layer to be measured is measured at any 10 points, and these averages Calculated by calculating the value.

Softening temperature: Of the laminated sheets, only the layer to be measured is formed alone in a film having a desired thickness (that is, the thickness of the layer to be measured in the laminated sheet), and the desired size is obtained. The film is cut into pieces (5 mm square in the following example), and the obtained film is measured using a needle intrusion method (load 100 mN, needle diameter: φ 1 mm, heating rate: 5 ° C./minute) by thermomechanical analysis (TMA) Do. In addition, 10 films are produced about each layer, it measures, and it calculates | requires by computing these average values.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1
[Preparation of pattern layer ink]
(Formulation of pigment mother liquor)
1) Carbon black pigment; 15 parts by mass (trade name "NIPex 35", Evonik Degussa Japan Co., Ltd.)
2) Dispersing agent; 7.5 parts by mass (trade name "SOLSPERSE 32000", Nippon Lubrizol Corporation)
3) Reactive monomer; 77.5 parts by mass (trade name "SR9003", propoxylated (2) neopentyl glycol diacrylate, Sartmar Japan Ltd.)
A pigment mother liquor was prepared by mixing the above materials with a mixer.

(Prescription of pattern layer ink)
1) Pigment mother liquor prepared above; 13 parts by mass 2) Aliphatic urethane acrylate oligomer; 10 parts by mass (trade name "CN 996", Arkema Co., Ltd.)
3) Tetrahydrofurfuryl acrylate; 10 parts by mass (trade name "V # 150", Osaka Organic Chemical Industry Co., Ltd.)
4) acrylic morpholine; 60 parts by mass
(Product name "ACMO", Kojin Co., Ltd.)
5) 2- (1,2-cyclohexanedicarboximide) ethyl acrylate; 5 parts by mass (trade name "ALONIX M-140", Toagosei Co., Ltd.)
6) 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 5 parts by mass (trade name “Darocure 1173”, BASF Corporation)
7) Bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide); 5 parts by mass (trade name “IRGACURE 819”, BASF Corporation)
The above materials were mixed by a mixer to produce a picture layer ink.

  The transparent film (75 micrometers in thickness, 95% of light transmittance (400-700 nm), softening temperature 100 degreeC) which consists of acrylic resin as a resin layer was used.

  A polyester-based resin was applied to one side of the resin layer with a reverse roll coater, and treated with a dryer to form a polyester resin layer. Thereafter, indium was attached to the surface of the polyester resin layer by vacuum deposition to form a metal deposition layer, thereby forming a composite colored layer.

  Next, a sheet made of an acrylonitrile butadiene styrene resin was laminated on the surface of the composite colored layer by heat lamination to form a backing layer.

  On the resin layer side of this laminate, that is, on the other side of the resin layer, a wood grain pattern was imparted by the printing equipment of the serial type ink jet method, using the pattern layer ink prepared above. After the application, ultraviolet rays were irradiated using an ultraviolet lamp to cure the ink, and a wood grain pattern layer having a curved surface with an uneven surface shape was formed. Thus, a laminated sheet was obtained. The thickness of the composite colored layer of the obtained laminated sheet is 30 μm, the light transmittance is 5% (400 to 700 nm), the softening temperature is 100 ° C., the thickness of the backing layer is 250 μm, the light transmittance is 0% (400 to 700 nm), the softening temperature was 70 ° C. The printing conditions and the ultraviolet irradiation conditions are as follows.

(Printing conditions)
Head heating temperature: 57 ° C
Nozzle diameter: 70 μm
Applied voltage: 50V
Pulse width: 15 μs
Drive frequency: 4.5 kHz
Resolution: 720 dpi
Pattern: Wood pattern

(UV irradiation condition)
Lamp type: Metal halide lamp Lamp output: 120 W / cm
Irradiation time: 1 second Irradiation frequency: 20 times Irradiation distance: 5 mm

  The application conditions for forming the pattern layer having a concavo-convex curved surface with a wood grain pattern are as follows. First, a wood grain pattern 8 as shown in FIG. 6 (a) is read by a scanner, and the read image is converted to gray scale (see FIG. 6 (b)). The digital image data was created and used by changing the portion with high brightness so as to reduce the thickness. For example, the cross section A-A 'in FIG. 6B is subdivided into the rectangles 9 with a minute width of 35 μm as shown in FIG. 7, and the rectangles 9 with this minute width have a height change of 10 to 100 μm. The ink was printed by an ink jet printing system to control the application amount. Thus, the thickness of the pattern layer is changed, and the dark portion has a large thickness and the light portion has a small thickness. The thickness of the pattern layer formed by ultraviolet irradiation after printing was continuously changed, and the surface was a smooth curved surface. That is, the picture layer had a shape in which a plurality of curves having different radii of curvature at the upper side in any cross section are connected, and the cross sectional shape and the cross sectional area of any cross section changed continuously. The light transmittance (400 to 700 nm) of the laminate of the resin layer and the pattern layer is that the portion giving the sense of depth has a range of 20 to 85%, and the portion having no sense of depth is 3 8%. The softening temperature of the picture layer was 150 ° C. Moreover, the curvature radius of the some curve which comprises the upper side of the cross section of a pattern layer was 35 micrometers-80 mm. Moreover, the thickness (average thickness in arbitrary ten places) of the pattern layer was 70 μm, the thinnest portion was 10 μm, and the thickest portion was 100 μm.

  Next, it was pre-shaped by vacuum pressure forming so that the picture layer of the laminated sheet was on the surface side of the molded body, to obtain a shaped body along the inner surface of the injection mold cavity. The unnecessary portion of the shaped body was cut and set along the inner surface of the injection mold cavity, and the resin was injected to the backing layer side to obtain a molded body in which the laminated sheet is integrated with the molded resin layer. In addition, as injection molding conditions, resin which forms a molding resin layer is resin temperature 260 degreeC, mold temperature 40 degreeC, and the molding pressure of 200 MPa using Teijin Chemical Co., Ltd. polycarbonate and ABS material alloy material T-2711. A molding was obtained under the conditions. The obtained molded product has a smooth surface, and a three-dimensional effect and its change due to a change in thickness of the pattern layer, and a sense of depth due to a composite visual change due to the overlap of the pattern layer and the colored layer can be obtained. It had a novel and innovative design in which the wood grain pattern of the natural product was given a metallic luster.

Comparative Example 1
A laminated sheet and a molded body were obtained in the same manner as in Example 1 except that the softening temperature of the picture layer was 33 ° C. The obtained molded product was not smooth on the surface but remained uneven (see FIG. 8). It was not possible to say that there is no sense of depth that occurs due to the combined action of the design layer and the colored layer due to the remaining unevenness, and that the designability is excellent. In addition, the preparation methods of the ink used in order to provide a pattern layer at this time are shown below.

[Preparation of Pattern Layer Ink of Comparative Example 1]
(Prescription of pattern layer ink)
1) Same pigment mother liquid as Example 1; 13 parts by mass 2) Aliphatic urethane acrylate oligomer; 10 parts by mass (trade name "CN996", Arkema Co., Ltd.)
3) Tetrahydrofurfuryl acrylate; 50 parts by mass (trade name "V # 150", Osaka Organic Chemical Industry Co., Ltd.)
4) Acrylic morpholine; 20 parts by mass (trade name "ACMO", Kojin Co., Ltd.)
5) 2- (1,2-cyclohexanedicarboximide) ethyl acrylate; 5 parts by mass (trade name "ALONIX M-140", Toagosei Co., Ltd.)
6) 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 5 parts by mass (trade name “Darocure 1173”, BASF Corporation)
7) Bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide; 5 parts by mass (trade name "IRGACURE 819", BASF Corporation)
The above materials were mixed by a mixer to produce a picture layer ink.

Comparative Example 2
A laminated sheet and a molded body were prepared in the same manner as in Example 1 except that a transparent film (thickness 200 μm, light transmittance 88% (400 to 700 nm), softening temperature 150 ° C.) made of polycarbonate resin was used as a resin layer. Obtained. The resulting molded product was not smooth on the surface but remained uneven (see FIG. 9). It was not possible to say that there is no sense of depth that occurs due to the combined action of the design layer and the colored layer due to the remaining unevenness, and that the designability is excellent.

  As can be seen from the above results, the molded product obtained by the present embodiment had a smooth surface, and the design layer was excellent in the three-dimensional effect, its change, and the designability in which a sense of depth was felt.

DESCRIPTION OF SYMBOLS 1 ... lamination sheet, 2 ... resin layer, 3 ... coloring layer, 4 ... backing layer, 5 ... picture layer, 6 ... molding resin layer, 7 ... molded object, a, g ... micro section, 8 ... grain pattern, 9 ... Small width rectangle

Claims (8)

A resin layer having light transmittance and having a softening temperature of 120 ° C. or less;
A colored layer laminated on one surface of the resin layer and having a softening temperature of 120 ° C. or less;
A backing layer laminated on the colored layer and having a softening temperature of 120 ° C. or less;
And a light transmitting layer made of an ionizing radiation curable resin, laminated on the other surface of the resin layer, and having a softening temperature of 140 to 160 ° C., and the surface of the light receiving layer is The thickness has been changed continuously by forming an uneven surface shape,
Laminated sheet characterized by   The picture layer has a cross-section of the picture layer cut in the thickness direction and has a shape in which a plurality of curves having different curvature radii at the upper side of the picture layer are connected, and a cross section of the picture layer in a plurality of cross sections parallel to each other The laminated sheet according to claim 1, which has a different shape.   The laminated sheet according to claim 2, wherein in the picture layer, cross-sectional areas of a plurality of cross sections parallel to each other are different.   The laminated sheet according to any one of claims 1 to 3, wherein the colored layer has glitter. A colored layer having a softening temperature of 120 ° C. or less and a backing layer having a softening temperature of 120 ° C. or less are sequentially laminated on one surface of a resin layer having light permeability and a softening temperature of 120 ° C. or less,
Thereafter, an ionizing radiation curable resin ink is applied to the other surface of the resin layer, and the ionizing radiation curable resin ink is irradiated with ionizing radiation to have light transparency and a softening temperature of 140 to 160 ° C. A method for producing a laminated sheet, comprising: forming a picture layer whose surface has a concavo-convex surface shape and thickness is continuously changed.   The laminated sheet according to any one of claims 1 to 4 and a molded resin layer integrated with the laminated sheet, the surface of the pattern layer is smooth, and the backing layer is the molded resin. A molded body characterized by being in contact with a layer.   The boundary surface between the picture layer and the resin layer, the boundary surface between the resin layer and the colored layer, and the boundary surface between the colored layer and the backing layer have a concavo-convex shape parallel to each other. The molded object according to claim 6, characterized in that   The method according to claim 6 or 7, wherein the laminated sheet is disposed in a mold cavity with the picture layer side facing the mold cavity surface, and the resin on the backing layer side of the laminated sheet. And molding the molded resin layer while pressing the picture layer side against the mold cavity surface.